Vulcanization accelerator



Patented Jan. 9, 1934 UNITED STATES PATENT OFFICE VULCANIZATION ACCELERATOR Ewald Zaucker and Max Biigemann, Cologne- Mulheim, and Ludwig Orthner, Leverkusen- I. G. Werk, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-om the-Main, Germany No Drawing. Application March 9, 1932, Serial No 597,806, and in Germany March 11, 1931- 18 Claims. (01. 18-53)' The present invention relates to new vucaniza- R tion accelerators, to a process of vulcanizing rubher and to the vulcanization products obtained N=C S N\ with the aid of the said new vulcanization accel- R1 5 erators. P

In accordance with the invention rubber is vulcanized after having incorporated therewith in any desired manner a substance containing the radical 1: C 1 l, 10 alkyl (ary aralkyl) 0 s .N\ I NN\ /R v 0 \CSN wherein a: and y mean vicinal carbon atoms of an 15 aromatic nucleus (benzene or naphthalene nucleus, for example) or as means nitrogen and y sulfur, oxygen or the group. R and R1 in the above formulae may stand, for

It is the idea of the invention to have found example for Similar or fitssimilar alkyl amlkyl that organic compounds containing the above or hydmaryl groups or may repres.ent 20 grouping are valuable vulcanization accelerators, chain alkylene fi may be Inter possessing an especially good critical temperamp ed y Oxygen or 6 group ture. The new accelerators, furthermore, can be applied with vulcanization accelerators of other types without the good critical temperature being 25 substantially impaired.

The following formulae are intended to show some types of compounds possessing the above mentioned grouping, without being limitative:- gherefore, may be represented for example 30 (\C S N/ /alkyl (rriattllgi,y 1:22:51), propyl, lsopropyl, normal-butyl,

l SN

l, alkyl u CH2 40 HzO-N R ore-O :CS-N/ SN 0 45 N R H1 H2 /CS-N/ s 0 50 OSN\ s ENDED R1 55 etc.

Obviously all the compounds in question may be substituted in the most various manner by a monovalent substituents, such as halogen atoms,

alkyl groups, nitro groups, hydroxy groups, alkoxy groups, amino groups, the carboxylic acid group etc. Ihe preparation of our new accelerators may be performed according to various methods. For example,

I. A metal salt (alkali metal salt, for example) of a compound containing the grouping is caused to react with a N-halogen amine containing the grouping o Hlg.N

in an aqueous or alcoholic solution, advantageously while gently heating. For example:

H2 Elk HzNOl+NaS@CHa NaCl l Hz Hz Hz Hg 1 +Hz- NSOH3 II. A compound containing the grouping C.S.Hlg o is caused to react with a compound containing the grouping in an aqueous medium or another suitable solvent, such as alcohol, acetone, etc., advantageously While cooling. For example:

CH3 GH2 OH2 OH2 III. A compound containing the grouping is caused to react with a compound containing the grouping (The letters a: and y in the above groupings are to be explained as mentioned on page 1.)

For vulcanization purposes the new vulcanization accelerators may be incorporated Within rubber in any desired manner, for example, by

rolling or' kneading. A vulcanizing agent, such as sulfur, selenium, aromatic nitro compounds+ metal oxides, are added to the vulcanization mixture together with or apart from the new vulcanization accelerators, and, if desired, filling materials (zinc oxide, carbon black etc.), plasticizing agents (stearic acid, tar etc.) and other ingredients known to favorably influence vulcanization processes or to improve the properties of the vulcanization products.

Vulcanization of the mixture is then performed by heating the same 'to temperatures usually applied in.vu1canization processes (HO-150 C. for example), until vulcanization is complete.

It may be mentioned that the term rubber as used in the disclosure and in the claims is intended to include as well natural rubber as the various artificial rubber-like masses obtainable, for example, by polymerizing butadiene, isoprene, dimethylbutadienes, chlorobutadiene etc. alone or in admixture with other polymerizable com pounds, such as styrene, vinylnaphthalene, acrylic acid derivatives, unsaturated ketones etc.

The following examples illustrate the invention without restricting it thereto, the parts being by weight:-

Example 1 orthonitrophenylsulfurchloride diethanolamine, orthoor para nitrophenylsulfurchloride+methylbenzylamine orthoor para-nitrophenylsulfurohloride methylethylamine thiocresol+N-chloropiperidine, 2-mercapto-4-phenyl-1.3.4-thiodiazole --5 thion N-chloropiperidine, 2mercaptobenzothiazole+N-chloropiperidine, 2-mercaptobenzothiazole+N-chloromorpheoline, Z-mercaptobenzothiazole+N-chlorodimethylamine, 2mercaptobenzothiazole+N-chlorodibutylamine, 2mercaptothiazoline+N-chloropiperidine, 2-mercaptoimidazoline N-chlorodimethylamine, 2-znercapto-4-phenyl-1.3.4-thiodiazoline N chlorodibutylamine, 2 mercaptobenzoxazole N-chloropiperidine, 2-mercaptobenzimidazole N-chloropiperidine, 6-nitro-2- mercaptobenzothiazole N-chloropiperidine, 6- dimethylamino 2 mercaptobenzothiazole N chloropiperidine, mercaptobenzometathiazone+ N-chlorodimethylamine, 2-mercapto-4-phenyl-5- methyl-1.3.4-thiodiazoline+N-chloropiperidine.

We claim:--

1. Vulcanization accelerators consisting of organic compounds containing the grouping:-

wherein at and y mean vicinal carbon atoms of an aromatic nucleus, or a: means nitrogen and y sulfur, oxygen or the NHgroup.

2. Vulcanization accelerators consisting of compounds of the probable formula:-

wherein R and R1 mean alkyl groups containing one to 4 carbon atoms or the benzyl group, or R and R1 jointly stand for the group CH2C.H2-CH2CH2CH2.

4. Vulcanization accelerator consisting of the compound of the probable formula:-

5. Vulcanization accelerator consisting of the compound of the probable formula:-

6. Vulcanization accelerator consisting of the compound of the probable formula:

N CH2. om. CH1. CH3

7. The process which comprises incorporating within rubber a vulcanizing agent and a vulcanization accelerator as claimed in claim 1 and vulcanizing the mixture.

8. The process which comprises incorporating within rubber sulfur and a vulcanization accelerator as claimed in claim 2 and vulcanizing the mixture.

9. The process which comprises incorporating within rubber sulfur and a vulcanization accelerator as claimed in claim 3 and vulcanizing the mixture.

10. The process which comprises incorporating within rubber sulfur and a vulcanization accelerator as claimed in claim 4 and vulcanizing the mixture.

11. The process which comprises incorporating within rubber sulfur and a vulcanization accelerator as claimed in claim 5 and vulcanizing the mixture.

12. The process which comprises incorporating within rubber sulfur and a vulcanization accelerator as claimed in claim 6 and vulcanizing the mixture.

13. A vulcanized rubber derived from natural rubber or an artificial rubber-like mass combined with a vulcanizing agent and a vulcanization accelerator as claimed in claim 1.

CH2. CH2. om. 0H3.

14. A vulcanized rubber derived from natural rubber combined with sulfur and a vulcanization accelerator as claimed in claim 2.

15. A vulcanized rubber derived from natural 5 rubber combined with sulfur and a vulcanization accelerator as claimed in claim 3.

16. A vulcanized rubber derived from natural rubber combined with sulfur and a vulcanization accelerator as claimed in claim 4. 

